Detergent compositions containing a smectite-type clay softening agent

ABSTRACT

Granular, built laundry detergent compositions containing particular smectite clay materials and quaternary ammonium antistatic agents. The compositions impart a soft hand and reduce the static charge of fabrics washed therein.

United States Patent [191 Nirschl et al.

[451 Jan. 21, 1975 DETERGENT COMPOSITIONS CONTAINING A SMECTITE-TYPECLAY SOFTENING AGENT Inventors: Joseph Peter Nirschl; Robert AndrewGloss, both of Cincinnati, Ohio The Proctor & Gamble Company,Cincinnati, Ohio Filed: Nov. 10, 1972 Appl. No.: 305,416

Assignee:

U.S. Cl 252/528, 252/8.6, 252/8.8,

252/113, 252/131 Int. Cl ..Cl1d 3/10 Field of Search 252/8.6, 8.8, 113,131,

[56] References Cited UNITED STATES PATENTS 3,716,488 2/1973 Kolsky et242/120 X 3,765,911 10/1973 Knowles et a1. 252/131 X PrimaryExaminer-Leland A. Sebastian Attorney, Agent, or Firm-Richard C. Wittc;Thomas H. OFlaherty; Jack D. Schaeffer [57] ABSTRACT Granular, builtlaundry detergent compositions containing particular smectite claymaterials and quaternary ammonium anti-static agents. The compositionsimpart a soft hand and reduce the static charge of fabrics washedtherein.

11 Claims, No Drawings DETERGENT COMPOSITIONS CONTAINING A SMECTITE-TYPECLAY SOFTENING AGENT BACKGROUND OF THE INVENTION The instant inventionrelates to qranular built laundry detergent compositions which providesimultaneous laundering, softening and anti-static benefits on textilesduring conventional fabric laundering operations. Such compositionsemploy a combination of synthetic detergent compounds, organic orinorganic detergent builders, particular smectite clay compounds havingparticular cation exchange characteristics and cationic anti-staticagents.

Various clay materials have been utilized in many different types ofdetergent systems for widely diverse purposes. Clays, for example, havebeen disclosed for utilization as builders (Schwartz and Perry, SurfaceActive Agents, lnterscience Publishers, Inc., 1949, pp. 232 and 299); aswater-softeners (British Pat. No. 461,221); as anti-caking agents (US.Pat. Nos. 2,625,513 and 2,770,600); as suspending agents (US. Pat. Nos.2,594,257, 2,594,258 and 2,920,045); and as fillers (US. Pat. No.2,708,185).

It is also well known that some clay materials can be deposited onfabrics to impart softening properties thereto. Such clay deposition isusually realized by contacting fabrics to be so treated with aqueousclay suspensions (see, for example, US. Pat. Nos. 3,033,699 and3,594,221). The copending application of Storm and Nirschl, Ser. No.271,943, filed July 14, 1972, and Ohren, Ser. No. 279,127, filed Aug. 9,1972, relate to the use of clays as softeners in laundry compositions.

While the use of clays as fabric softeners is described in the citedart, such clay softeners are not entirely suitable for this purposesince they do not possess antistatic properties. Commercially acceptablesofteners provide anti-static benefits, and such benefits have come tobe expected by the user of such products. Indeed, fabrics coated withclays, while exhibiting a soft hand, tend to develop higher levels ofstatic charge than the uncoated fabrics.

Various quaternary ammonium compounds known in the art possessanti-static properties, and the use of clays in combination with suchcationic agents for various purposes has been taught in the prior art.For example, U.S. Pat. No. 3,594,212 teaches that quaternary ammoniumcompounds affixed to the surface of clay enhances clay deposition onfabrics; see, also, US. Pat. No. 3,625,505. However, as will be seenhereinafter, when quaternary compounds are chemically affixed to claysurfaces in the manner disclosed in the prior art, the desirableanti-static benefit of the quaternary compounds is lost. Furthermore,such quaternary ammonium compounds are not generally taught to be usefulin combination with anionic surfactants in the manner disclosed herein.

US. Pat. No. 2,819,288 discloses clays in combination with cationicsurfactants as dry emulsifiers; however, these compositions do notcontain detergent compounds suitable for laundering fabrics.

Accordingly, while effective for their intended uses, the prior artcompositions containing clay-plusquaternary ammonium compounds are notsuitable for laundering fabrics while concurrently imparting softnessand anti-static benefits thereto.

The concurrently filed application of Nirschl and Gloss, entitled SoapCompositions, Ser. No.

305,417, filed Nov. 10, 1972, discloses the use ofclays and quaternarysalts in soap compositions.

It is an object of the present invention to provide compositions whichcan be employed to concurrently launder, soften, and impart anti-staticbenefits to fab rics.

It is a further object of this invention to provide combined laundering,softening and anti-static compositions in the form of granularformulations which are readily dispersible in aqueous laundry baths.

These and the objects are obtained herein, as will be seen from thefollowing disclosure.

SUMMARY OF THE lNVENTlON The present invention encompasses granularbuilt laundry detergent compositions comprising: (a) from about 2 toabout 30 percent by weight of a non-soap synthetic detergent compoundselected from the group consisting of anionic synthetic detergents,nonionic synthetic detergents, ampholytic synthetic detergents,zwitterionic synthetic detergents and mixtures thereof; (b) from about10 to about 60 percent by weight of an organic or inorganic detergentbuilder salt; (c) from about 1 to about 50. percent by weight of asmectitetype clay softening agent having an ion exchange capacity of atleast about 50 meq/l00 g; and (d) from about 0.5 to about 15 percent byweight of a substantially water-insoluble quaternary ammoniumanti-static agent of the formula, [R N R ],,X, wherein each R is ahydrocarbyl group containing from about 10 to about 22 carbon atoms andeach R is a hydrocarbyl group containing from about 1 to about 4 carbonatoms and werein X is an anion, e.g., halide, hydroxide, sulfate,carbonate, phosphate, etc. In the above formula, the superscript Itindicates the charge on the anion; n can be 1 to 3 in the compoundsherein. The weight ratio of smectite-type clay to quaternary ammoniumcompound in the compositions herein is from about 40:1 to about 1:1, andis preferably about 5:1. The quaternary ammonium compound is present inreleasable combination with the compositions herein. By releasablecombination is meant that, on admixture with water, the solublecomponents of the composition granules dissolve and the clay andquaternary compound are independently suspended in the aqueous medium.

The compositions herein preferably provide a solution pH of from about 7to about 12 when dissolved in water at a concentration of about 0.12percent by weight.

In a method aspect, the invention encompasses methods for concurrentlycleansing, softening and providing antistatic effects on fibers andfabrics comprising laundering said fibers or fabrics in an aqueouslaundry bath containing an effective amount (e.g., from about 0.02 toabout 2 percent by weight) of a laundry detergent composition asdescribed above.

DETAILED DESCRIPTION OF THE INVENTION The compositions and processes ofthis invention employ four essential ingredients: the water-solubledetergency compound; the detergency builder; the clay softener; and thequaternary ammonium anti-static agent. The detergency compound functionsin standard fashion to remove soil from fabrics being laundered. Thedetergency builder functions both to enhance the cleansing action of thedetergency compound and to uniformly disperse the clay softener. Thesmectite-type clay functions to soften the laundered fabrics. Thequaternary ammonium compound provides anti-static effects on the fabricsand adds an increment of softening benefits to the fabrics. Thesevarious components are described in greater detail hereinafter.

Anti-Static Agent The quaternary ammonium anti-static agents areemployed in the instant compositions at a concentration of from about0.5 to about 15 percent, preferably from about 0.5 to about percent byweight, and are therefore present in the laundering liquors at levelsfrom about 5 ppm to about 150 ppm. In general, the quaternary anti-statsare used at a clay-to-quaternary weight ratio of from about 40:1 toabout 1:1, preferably about 5:1.

The anti-static agents of this invention, are quaternary ammonium saltsof the formula wherein each R group is a hydrocarbyl (i.e., alkyl oralkenyl) group containing from about ID to about 22 car bon atoms andeach R group is a short-chain hydrocarbyl group containing from 1 toabout 4 carbon atoms. X in the above compounds can be any saltforminganion, e.g., halide, hydroxide, sulfate, carbonate, phosphate, etc. Thecharge on the anion is designated as n, where n is 1-3. The number ofcationic ammonium groups, n, will equal the charge, n, on the anion toprovide electrical neutrality. quaternary ammonium compounds wherein n=1are commercially available and are preferred herein for this reason.

The quaternary ammonium anti-static agents herein are characterized bytheir limited solubility in water. That is to say, such quaternary saltsare essentially insoluble in water, existing therein in what appears tobe the mesomorphic liquid crystalline state. The insolubility of thequaternary salts used herein is a critical aspect of this inventioninasmuch as water-soluble quaternary salts become chemically affixed tothe surface of the clay or react with the preferred anionic surfactants.When the quaternary anti-static agent is affixed to the surface of theclay, or has reacted with the anionic surfactant, it does not providethe desired antistatic effects on fabics.

The cause of the solubility properties of the particular class ofquaternaries found to be useful herein is not known with certainty.While not intending to be limited by theory, it appears that the twoextended hydrocarbyl chains (C -C present in the molecules serve tolower their solubility and probably account for their existence asliquid crystals. In any event, it has now been found the dilong chainquaternaries can be used in releasable combination with compositionscontaining clays. That is to say, the quaternary compound and the clayare independently suspended in the washing liquor and the quaternarycompound does not appear to substantially affix itself to the claysurface by an ion exchange mechanism.

Quaternary ammonium compoundsare not generally considered to be usefulin combination with anionic surfactants since the opposite charges onthese two types of compounds cause them to react and precipitate fromsolution. Yet, the anionics are a preferred class of surfactants forlaundering fabrics. Surprisingly, it has now been found that thedesirable anti-static effects of the insoluble quaternary ammonium compounds used herein are not negated when employed in combination withanionic surfactants. Apparently. the insoluble nature of the di-longchain quaternary compounds renders them somewhat compatible withanionics; whatever the reason, the quaternary ammonium anti-stats hereinperform their anti-static function when used in combination with claysand anionic surfactants.

The quaternary ammonium anti-static agents used in this invention can beprepared in various ways wellknown in the art. Many such materials arecommercially available. The quaternaries are often made front alkylhalide mixtures corresponding to the mixed alkyl chain lengths in fattyacids. For example, the ditallow quaternaries are made from alkylhalides having mixed C -C chain lengths. Such mixed di-long chainquaternaries are useful herein and are preferred from a cost standpoint.

As noted above, essentially any anionic group can be the counter-ion inthe quaternary compounds used herein. The anionic groups in thequaternary compounds can be exchanged, one for another, using standardanion exchange resins. Thus, quaternary ammonium salts having anydesired anion are readily available. While the nature of such anions hasno effect on the compositions and processes of this invention, chlorideion is the preferred counter-ion from a cost standpoint.

The following are representative examples of substantiallywater-insoluble quaternary ammonium antistatic agents suitable for usein the compositions and processes of the instant invention. All of thequaternary ammonium compounds listed can be formulated in rcleasablecombination with the detergent compositions herein, but the compilationof suitable quaternary compounds hereinafter is only by way of exampleand is not intended to be limiting of such compounds.Ditallowdimethylammonium chloride is an especially preferred quaternaryanti-static agent for use herein by virtue of its low cost, lowsolubility and high-anti-static activity; other useful di-long chainquaternary compounds are dicetyldimethylammonium chloride;bis-docosyldimethylammonium chloride; didecyldimethylammonium chloride;ditallowdimethylammonium bromide; dioleoyldimethylammonium hydroxide;ditallowdiethylammonium chloride; ditallowdipropylammonium bromide;ditallowdibutylammonium fluoride, cetyldecylmethylethylammoniumchloride, bis- [ditallowdimethylammonium lsulfate; tris-[ditallowdimethylammonium]-phosphate; and the like.

Synthetic Detergent From about 2 to about 30 percent by weight,preferably from about 5 to about 20 percent by weight, of the instantcompositions comprise a non-soap synthetic detergent selected from thegroup consisting of anionic synthetic detergents, nonionic syntheticdetergents, ampholytic synthetic detergents, and zwitterionic syntheticdetergents. Examples of synthetic detergents of these types aredescribed as follows:

Anionic Detergents Anionic synthetic detergents include watcr-solublesalts, particularly the alkali metal salts, of organic sulfuric reactionproducts having in their molecular structure an alkyl group containingfrom about 8 to about 22 carbon atoms and a moiety selected from thegroup consisting of sulfonic acid and sulfuric acid ester moieties.(Included in the term alkyl is the alkyl portion of higher acylmoieties.) Examples of this group of synthetic detergents which form apart of the preferred built detergent compositions of the presentinvention are the sodium and potassium alkyl sulfates, especially thoseobtained by sulfating the higher alcohols (C -C carbon atoms) producedby reducing the glycerides of tallow or coconut oil; sodium andpotassium alkyl benzene sulfonates, in which the alkyl group containsfrom about 9 to about 20 carbon atoms in straight chain orbranched-chain configuration, e.g., those of the type described in U.S.Pat. Nos. 2,220,099 and 2,477,383 (especially valuable are linearstraight chain alkyl benzene sulfonates in which the average of thealkyl groups is about 1 1.8 carbon atoms and commonly abbreviated as CLAS); sodium alkyl glyceryl ether sulfonates, especially those ethers ofhigher alcohols derived from tallow and coconut oil; sodium coconut oilfatty acid monoglyceride sulfonates and sulfates; sodium and potassiumsalts of sulfuric acid esters of the reaction product of one mole of ahigher fatty alcohol (e.g. tallow or coconut oil alcohols) and about 1to 6 moles of ethyl ene oxide; sodium and potassium salts of alkylphenol ethylene oxide ether sulfates with about 1 to about 10 units ofethylene oxide per molecule and in which the alkyl groups contain fromabout 8 to about 12 carbon atoms.

Anionic phosphate surfactants are also useful in the present invention.These are surface active materials having substantial detergentcapability in which the anionic solubilizing group connectinghydrophobic moieties is an oxy acid of phosphorus. The more commonsolubilizing groups, of course, are -SO,,H and SO H. Alkyl phosphateesters such as (RO) PO H and R0- PO H in which R represents an alkylchain containing from about 8 to about carbon atoms are useful herein.

These phosphate esters can be modified by including in the molecule fromone to about 40 alkylene oxide units, e.g., ethylene oxide units.Formulae for these modified phosphate anionic detergents are formula 0 nOCR CH CH SO M where R is alkyl of about 9 to about 23 carbon atoms(forming with the two carbon atoms an alkane group); R is alkyl of 1 toabout 8 carbon atoms; and M is a water-soluble cation.

The water-soluble cation, M, in the hereinbefore described structuralformula can be, for example, an alkali metal cation (e.g., sodium,potassium, lithium), ammonium or substituted-ammonium cation. Specificexamples of substituted ammonium cations include methyl-, dimethyl-, andtrimethylammonium cations and quaternary ammonium cations such astetramethyl-ammonium and dimethyl piperidinium cations and those derivedfrom alkylamines such as ethylamine, diethylamine, triethylamine,mixtures thereof, and the like.

Specific examples of beta-acyloxy-alkancl sulfonates, or alternatively2-acyloxy-alkanel sulfonates, useful herein include the sodium salt of 2acetoxy-tridecane-l-sulfonic acid; the potassium salt of2-propi0nyloxy-tetradecane-l-sulfonic acid; the lithium salt of2-butanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of2-pentanoyloxypentadccane-1- sulfonic acid; the sodium salt of2-acetoxy-hexadecancl-sulfonic acid; the potassium salt of2octanoyloxytetradecane-l-sulfonic acid; the sodium salt of 2-acetoxy-heptadecane-l-sulfonic acid; the lithium salt of2-acetoxy-octadecane-l-sulfonic acid; the potassium salt of2-acetoxy-nonadecane-l-sulfonic acid; the sodium salt of2-acetoxy-uncosane-1-sulfonic acid; the sodium salt of2-propionyloxy-docosanc-l-sulfonic acid; the isomers thereof.

Preferred beta-acyloxy-alkane-l-sulfonate salts herein are the alkalimetal salts of beta-acetoxy-alkanel-sulfonic acids corresponding to theabove formula wherein R is an alkyl of about 12 to about 16 carbonatoms, these salts being preferred from the standpoints of theirexcellent cleaning properties and ready availability.

Typical examples of the above described betaacetoxy alkanesulfonates aredescribed in the literature: Belgium Pat. No. 650,323 issued July 9,1963, discloses the preparation of certain 2-acyloxy alkanesulfonicacids. Similarly, U.S. Pat. Nos. 2,094,451 issued Sept. 28, 1937, toGuenther et al. and 2,086,215 issued July 6, 1937 to DeGroote disclosecertain salts of betaacetoxy alkanesulfonic acids. These references arehereby incorporated by reference.

Another preferred class of anionic detergent compounds herein, both byvirtue of superior cleaning properties and low sensitivity to waterhardness (Ca+land Mg-l-lions) are the alkylated a-sulfocarboxylates,containing about 10 to about 23 carbon atoms, and having the formula RII OR wherein R is C to C alkyl, M is a water-soluble cation ashereinbefore disclosed, preferably sodium ion, and R is short-chainalkyl, e.g., methyl, ethyl, propyl, and butyl. These compounds areprepared by the esterification of a-sulfonated carboxylic acids, whichare commercially available, using standard techniques. Specific examplesof the alkylated a-sulfocarboxylates preferred for use herein include:

ammonium methyl-a-sulfopalmitate,

triethanolammonium ethyl-a-sulfostearate,

sodium methyl-a-sulfopalmitate,

sodium ethyl-a-sulfopalmitate,

sodium butyl-a-sulfostearate,

potassium methyl-a-sulfolaurate,

lithium methyl-a-sulfolaurate, as well as mixtures thereof.

A preferred class of anionic organic detergents are the B-alkyloxyalkane sulfonates. These compounds have the following formula:

R H l 2 I R p g, .Jo rr where R is a straight chain alkyl group havingfrom 6 to 20 carbon atoms, R is a lower alkyl group having from I(preferred) to 3 carbon atoms, and M is a watersoluble cation ashereinbefore described.

Specific examples of Balkyloxy alkane sulfonates, or alternatively2-alkyloxy-alkane-l-sulfonates, having low hardness (calcium ion)sensitivity useful herein to provide superior cleaning levels underhousehold washing conditions include:

potassium-B-methoxydecanesulfonate,

sodium 2-methoxytridecanesulfonate,

potassium 2ethoxytetradecylsulfonate,

sodium 2-isopropoxyhexadecylsulfonate,

lithium 2-t-butoxytetradecylsulfonate,

sodium B-methoxyoctadecylsulfonate, and

ammonium B-n-propoxydodecylsulfonate.

Other synthetic anionic detergents useful herein are alkyl ethersulfates. These materials have the formula RO(C H.,O),SO M wherein R isalkyl or alkenyl of about 10 to about carbon atoms, x is 1 to 30, and Mis a watersoluble cation as defined hereinbefore. The alkyl ethersulfates useful in the present invention are condensation products ofethylene oxide and monohydric alcohols having about 10 to about 20carbon atoms. Preferably, R has 14 to 18 carbon atoms. The alcohols canbe derived from fats, e.g., coconut oil or tallow, or can be synthetic.Lauryl alcohol and straight chain alcohols derived from tallow arepreferred herein. Such alcohols are reacted with l to 30, and especially6, molar proportions of ethylene oxide and the resulting mixture ofmolecular species, having, for example, an average of 6 moles ofethylene oxide per mole of alcohol, is sulfated and neutralized.

Specific examples of alkyl ether sulfates of the present invention aresodium coconut alkyl ethylene glycol ether sulfate; lithium tallow alkyltriethylene glycol ether sulfate; and sodium tallow alkylhexaoxyethylene sulfate.

Preferred herein for reasons of excellent cleaning properties and readyavailability are the alkali metal coconutand tallow-alkyl oxyethyleneether sulfates having an average of about 1 to about 10 oxyethylenemoieties. The alkyl ether sulfates of the present invention are knowncompounds and are described in US Pat. No. 3,332,876, to Walker (July25, 1967), incorporated herein by reference.

Additional examples of anionic non-soap synthetic detergents which comewithin the terms of the present detergents, which come within the termsof the present invention, are the compounds which contain two anionicfunctional groups. These are referred to as dianionic detergents.Suitable di-anionic detergents are the disulfonates, disulfates, ormixtures thereof which may be represented by the following formulae:

where R is an acyclic aliphatic hydrocarbyl group hav ing 15 to 20carbon atoms and M is a water-solubilizing cation, for example, the C toC20 disodium 1,2- alkyldisulfates, C to Cdipotassium-l,2-alkyldisulfonates or disulfates, disodium l,9-hexadecyldisulfates, C to C disodium-l ,2-alkyldisulfonates, disodiuum1,9-stearyldisulfates and 6,lO-octadecyldisulfates.

The aliphatic portion of the disulfates or disulfonates is generallysubstantially linear, thereby imparting desirable biodegradableproperties to the detergent compound.

The water-solubilizing cations include the customary cations known inthe detergent art, i.e., the alkali metals, and the ammonium cations, aswell as other metals in group [1A, IIB, lllA, IVA and NE of the PeriodicTable except for boron. The preferred watersolubilizing cations aresodium or potassium. These di anionic detergents are more fullydescribed in British Letters Patent 1,151,392 which claims priority onan application made in the United States of America (No. 564,556) onJuly 12, 1966.

Still another anionic synthetic detergents include the class designatedas succinamates. This class includes such surface active agents asdisodium N-octadecylsulfosuccinamate; tetrasodium N-( l,2-dicarboxyethyl)-N- octadecylsulfo-succinamate; diamyl ester of sodiumsulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctylesters of sodium sulfosuccinic acid.

Other suitable anionic detergents utilizable herein are olefinsulfonates having about 12 to about 24 carbon atoms. The term olefinsulfonates" is used herein to mean compounds which can be produced bythe sulfonation of a-olefins by means of uncomplexed sulfur trioxide,followed by neutralization of the acid reaction mixture in conditionssuch that any sultones which have been formed in the reaction arehydrolyzed to give the corresponding hydroxy-alkanesulfonates. Thesulfur trioxide can be liquid or gaseous, and is usually, but notnecessarily, diluted by inert diluents, for example by liquid S0chlorinated hydrocarbons, etc., when used in the liquid form, or by air,nitrogen, gaseous S0 etc., when used in the gaseous form.

The a-olefins from which the olefin sulfonates are derived aremono-olefins having 12 to 24 carbon atoms, preferably 14 to 16 carbonatoms. Preferably, they are straight chain olefins. Examples of suitablel-olefins include l-dodecene; l-tetradecene; l-hexadecene; loctadecene;l-eicosene and l-tetracosene.

In addition to the true alkene sulfonates and a proportion ofhydroxy-alkanesulfonates, the olefin sulfonates can contain minoramounts of other materials, such as alkene disulfonates depending uponthe reaction conditions, proportion of reactants, the nature of thestarting olefins and impurities in the olefin stock and side reactionsduring the sulfonation process.

A specific anionic detergent which has also been found excellent for usein the present invention is described more fully in the U.S. Pat. No.3,332,880 of Phillip F. Pflaumer and Adrain Kessler, issued July 25,1967, titled Detergent Composition, the disclosure of which isincorporated herein by reference.

Of all the above-described types of anionic surfactants, preferredcompounds include sodium linear alkyl benzene sulfonate wherein thealkyl chain averages from about to 18, more preferably about 12, carbonatoms in length, sodium tallow alkyl sulfate;2-acetoxytridecane-l-sulfonic acid; sodium methyl-asulfopalmitate;sodium B-methoxyoctadecylsulfonate; sodium coconut alkyl ethylene glycolether sulfonate; the sodium salt of the sulfuric acid ester of thereaction product of one mole of tallow alcohol and three moles ofethylene oxide; and mixtures thereof.

Nonionic Synthetic Detergents Most commonly, nonionic surfactants arecompounds produced by the condensation of an alkylene oxide (hydrophilicin nature) with an organic hydrophobic compound which is usuallyaliphatic or alkyl aromatic in nature. The length of the hydrophilic ofpolyoxyalkylene moiety which is condensed with any particularhydrophobic compound can be readily adjusted to yield a water-solublecompound having the desired degree of balance between hydrophilic andhydrophobic elements. Another type of nonionic surfactants are theso-called polar nonionics derived from amine oxides, phosphine oxides orsulfoxides. Examples of suitable nonionic surfactants include:

1. The polyethylene oxide condensates of alkyl phenols. These compoundsinclude the condensation products of alkyl phenols having an alkyl groupcontaining from about 6 to 12 carbon atoms in either a straight chain orbranched chain configuration, with ethylene oxide, the said ethyleneoxide being present in amounts equal to 5 to 25 moles of ethylene oxideper mole of alkyl phenol. The alkyl substituent in such compounds may bederived, for example, from polymerized propylene, diisobutylene, octene,or nonene. Examples of compounds of this type include nonyl phenolcondensed with about 9.5 moles of ethylene oxide per mole of nonylphenol, dodecyl phenol condensed with about 12 moles of ethylene oxideper mole of phenol, dinonyl phenol condensed with about moles ofethylene oxide per mole of phenol, di-isooctylphenol condensed withabout 15 moles of ethylene oxide per mole of phenol. Commerciallyavailable nonionic surfactants of this type include lgepal CO-6l0marketed by the GAP Corporation; and Triton X-45, X-l l4, X-100 and X-102, all marketed by the Rohm and Haas Company.

2. The condensation products of aliphatic alcohols with ethylene oxide.The alkyl chain of the aliphatic alcohol may either be straight orbranched and generally contains from about 8 to about 22 carbon atoms.Examples of such ethoxylated alcohols include the condensation productof about 6 moles of ethylene oxide with 1 mole of tridecanol, myristylalcohol condensed with about 10 moles of ethylene oxide per mole ofmyristyl alcohol, the condensation product of ethylene oxide withcoconut fatty alcohol wherein the coconut alcohol is a mixture of fattyalcohols with alkyl chains varying from 10 to 14 carbon atoms andwherein the condensate contains about 6 moles of ethylene oxide per moleof alcohol, and the condensation product of about 9 moles of ethyleneoxide with the abovedescribed coconut alcohol. Examples of commerciallyavailable nonionic surfactants of this type include Tergitol l5-S-9marketed by the Union Carbide Corporation, Neodol 23-65 marketed by theShell Chemical Company and Kyro EOB marketed by the Procter & GambleCompany.

3. The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol. Thehydrophobic portion of these compounds has a molecular weight of fromabout 1,500 to 1,800 and of course exhibits water insolubility. Theaddition of polyoxycthylene moieties to this hydrophobic portion tendsto increase the water-solubility of the molecule as a whole, and theliquid character of the product is retained up to the point where thepolyoxyethylene content is about 50% of the total weight of thecondensation product. Examples of compounds of this type include certainof the commercially available Pluronic surfactants marketed by theWyandotte Chemicals Corporation.

4. The condensation products of ethylene oxide with the productresulting from the reaction of propylene oxide and ethylene diamine. Thehydrophobic base of these products consists of the reaction product ofethylene diamine and excess propylene oxide, said base having amolecular weight of from about 2,500 to about 3,000. This base iscondensed with ethylene oxide to the extent that the condensationproduct contains from about 40 to about percent by weight ofpolyoxyethylene and has a molecular weight of from about 5,000 to about11,000. Examples of this type of nonionic surfactant include certain ofthe commercially available Tetronic compounds marketed by the WyandotteChemicals Corporation.

5. Surfactants having the formula RR RN O (amine oxide surfactants)wherein R is an alkyl group containing from about 10 to about 28 carbonatoms, from 0 to about 2 hydroxy groups and from 0 to about 5 etherlinkages, there being at least one moiety of R' which is an alkyl groupcontaining from about 10 to about 18 carbon atoms and no ether linkages,and each R and R is selected from the group consisting of alkyl groupsand hydroxyalkyl groups containing from 1 to about 3 carbon atoms,

Specific examples of amine oxide surfactants include:dimethyldodecylamine oxide, dimethyltetradecylamine oxide,ethylmethyltetradecylamine oxide, cetyldimethylamine oxide,dimethylstearylamine oxide, cetylethylpropylamine oxide,diethyldodecylamine oxide, diethyltetradecylamine oxide,dipropyldodecylamine oxide, bis-(Z-hydroxyethyl)dodecylamine oxide, bis-(2-hydroxyethyl)-3-dodecoxy-l-hydroxypropylamine oxide,(2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleylamine oxide,dimethyl-(2- hydroxydodecyl)amine oxide, and the corresponding decyl,hexadecyl and octadecyl homologs of the above compounds.

6. Surfactants having the formula RR R P O (phosphine oxide surfactants)wherein R is an alkyl group containing from about 10 to about 28 carbonatoms, from 0 to about 2 hydroxy groups and from 0 to about 5 etherlinkages, there being at least one moiety of R which is an alkyl groupcontaining from about 10 to about 18 carbon atoms and no ether linkages,and each R and R is selected from the group consisting of alkyl groupsand hydroxyalkyl groups containing from 1 to about 3 carbon atoms.

Specific examples of the phosphine oxide detergents include:dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide,ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide,dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide,diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide,dipropyldodecylphosphine oxide, dipropyldodecylphosphine oxide,bis-(hydroxymethyl)- dodecylphosphine oxide,bis-(2-hydroxyethyl)dodecylphosphine oxide,(2-hydroxypropyl)methyltetradecylphosphine oxide, dimethyloleylphosphineoxide, and dimethyl-(2-hydroxy-dodecyl)phosphine oxide and thecorresponding decyl, hexadecyl, and octadecyl homologs of the abovecompounds.

7. Surfactants having the formula (sulfoxide surfactants) wherein R isan alkyl group containing from about 10 to about 28 carbon atoms, fromto about ether linkages and from 0 to about 2 hydroxyl substituents, atleast one moiety of R being an alkyl group containing no ether linkagesand containing from about to about 18 carbon atoms, and wherein R is analkyl group containing from 1 to 3 carbon atoms and from zero to twohydroxyl groups. Specific examples of sulfoxide surfactants includeoctadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradecyl methylsulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-methoxytridecyl methylsulfoxide, 3-hydroxy- 4-dodecoxybutyl methyl sulfoxide, octadecyl 2-hydroxyethyl sulfoxide, and dodecylethyl sulfoxide.

Of all the above-described types of nonionic surfactants, preferrednonionic surfactants include the condensation product of nonyl phenolwith about 9.5 moles of ethylene oxide per mole of nonyl phenol, thecondensation product of coconut fatty alcohol with about 6 moles ofethylene oxide per mole of coconut fatty alcohol, the condensationproduct of tallow fatty alcohol with about 1 1 moles of ethylene oxideper mole of tallow fatty alcohol and the condensation product of asecondary fatty alcohol containing about carbon atoms with about 9 molesof ethylene oxide per mole of fatty alcohol.

Ampholytic Synthetic Detergents Ampholytic synthetic detergents can bebroadly described as derivatives of aliphatic or aliphatic derivativesof heterocyclic secondary and tertiary amines in which the aliphaticradical may be staight chain or branched and wherein one of thealiphatic substituents contains from about 8 to 18 carbon atoms and atleast one contains an anionic water-solubilizing group, e.g.,

carboxy, sulfonate, sulfato. Examples of compounds falling within thisdefinition are sodium 3- (dodecylamino)-propionate, sodium 3-(dodecylamino)propanel -sulfonate, sodium 2- (dodecylamino)ethylsulfate, sodium 2- (dimethylamino)octadecanoate, disodium 3-(N-carboxyme'thyldodecylamino)-propane-l-sulfonate, disodiumoctadecyl-iminodiazetate, sodium l-carboxymethyl-Z-undecylimidazole, andsodium N,N bis(2- hydroxyethyl)-2-sulfato-3-dodecoxypropylamine. Sodium3-(dodecylamino)propane-l-sulfonate is preferred.

Zwitterionic Synthetic Detergents containing from about 3 to 18 carbonatoms and at least one aliphatic substituent containing an anionicwater-solubilizing group, e.g., carboxy, sulfonate, sulfato, phosphato,or phosphono. Examples of various classes of Zwitterionic surfactantsoperable herein are described as follows:

1. Compounds corresponding to the general formula wherein R is alkyl,alkenyl or a hydroxyalkyl containing from about 8 to about 18 carbonatoms and containing if desired up to about 10 ethylene oxide moietiesand/or a glyceryl moiety; Y, is nitrogen, phosphorus or sulfur, R isalkyl or monohydroxyalkyl containing 1 to 3 carbon atoms; x is 1 when Yis S, 2 when Y vis N or P; R is alkylene or hydroxyalkylene containingfrom 1 to about 5 carbon atoms; and Z is a carboxy, sulfonate, sulfate,phosphate or phosphonate group. Examples of this class of Zwitterionicsurfactants include 3-(N,N-dimethyl-N-hexadecylammonio )-propanelsulfonate; 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate; 2-(N,N-dimethyl-N- dodecy'lammonio)ace tate;3-(N,N-dimethyl-N- dodecylammonio)propionate; 2-(N,N-dimethyl-N-octadecylammonio)ethane-l-sulfate; 3-(P,P-dimethyl-P-dodecylphosphonio)propane-lsulfonate; 2(S-methyl-S-tert-hexadecylsulfonio)ethane-1-sulfonate;3-(S-methyl-S-dodecylsulfonio)propionate; 4-(S-methyl-S-tetradecylsulfonio)butyrate; 3-(N,N-dimethyl-N-4-dodecenylammonio)propane-1- sulfonate; 3-(N,N-dimethyl-N-2-.diethoxyhexadecylam monio )propane-l -phosphate;

and 3-(N,N-dimethyl-N-4-glyceryldodecylammonio)- propionate.

Preferred compounds of this class from a commercial standpoint are3-(N,N-dimethyl-N- hexadecylammonio)-2-hydroxypropanel -sulfonate;3-(N,N-dimethyl-N-alkylammonio)-2- hydroxypropane-l-sulfonate; the alkylgroup being derived from tallow fatty alcohol; 3-(N,N-dimethyl-N-hexadecylammonio )propanel -sulfonate; 3-( N ,N-dimethyl-N-tetradecylammonio)propanel -sulfonate;3-(N,N-dimethyl-N-alkylammonio-Z-hydroxypropanel-sulfonate, the alkylgroup being derived from the middle cut of coconut fatty alcohol;3-(N,N- dimethyldodecylammonio )-2-hydroxypropanesulfonate;4-(N,N-dimethyltetradecylammonio)butane-l-sulfonate; 4-(N,N-dimethyl-N-hexadecylammonio)butane-Lsulfonate;4-(N,N-dimethyl-hexadecylammonio)butyrate;(N,N-dimethyl-N-octadecylammonio)hexanoate;

13 (N,N-dimethyl-N-eicosylammonio)-3-methylpropanel-sulfonate; and6-(N,N-dimethyl-N- hexadecylammonio)hexanoate.

Means for preparing many of the surfactant compounds of this class aredescribed in US. Pat. Nos. 2,129,264, 2,774,786, 2,813,898, 2,828,332and 3,529,521 and; German Pat. No. 1,018,421 all incorporated herein byreference.

2. Compounds having the general formula:

wherein R is an alkyl, cycloalkyl, aryl, aralkyl or alkaryl groupcontaining from 10 to 20 carbon atoms; M is a bivalent radical selectedfrom the group consisting of aminocarbonyl, carbonylamino, carbonyloxy,aminocarbonylamino, the corresponding thio groupings and substitutedamino derivatives; R and R are alkylene groups containing from 1 to 12carbon atoms; R is alkyl or hydroxyalkyl containing from 1 to carbonatoms; R, is selected from the group consisting of R groups R,,-MR and RCOOMe wherein R R R and R are as defined above and Me is a monovalentsalt-forming cation. Compounds of the type include N,-N-bis(oleylamidopropyl)-N-methyl-N-carboxymethylammonium betaine;N,N-bis(stearamidopropyl-N- methyl-N-carboxymethylammonium betaine; N-(stearamidopropyl)-N-dimethyl-N-carboxymethylammonium betaine;N,N-bis(oleylamidopopy1)-N-(2- hydroxyethyl)-N-carboxylmethylammoniumbetaine; and N-Nbis-(stearamidopropyl)-N-(2-hydroxyethyl)-N-carboxymethylammonium betaine. Zwitterionic surfactants of this typeare preparing in accordance with methods described in US. Pat. No.3,265,719 and DAS 1,018,421.

3. Compounds having the general formula:

R9 cu (CI-I CH so wherein R is an alkyl group, R is a hydrogen atom oran alkyl group, the total number of carbon atoms in R and R being from 8to 16 and o i 2 R 11 12 13 wherein R is an alkarylmethylene groupcontaining from about 8 to 24 carbon atoms in the alkyl chain; R isselected from the group consisting of R groups and alkyl andhydroxyalkyl groups containing from 1 to 7 carbon atoms; R is alkyl orhydroxylakyl containing from 1 to 7 carbon atoms; R is alkylene orhydroxyalkylene containing from 1 to 7 carbon atoms and Z is selectedfrom the group consisting of sulfonate. carboxy and sulfate. Examples ofzwitterionic surfactants of this type include 3-(N-d0decylbenzyl-N,N-dimethylammonio)propane-l -sulfonate; 4-( N-dodecylbenzyl-N,N-dimethylammonio)butanel sulfonate;3-(N-hexadecylbenzyl-N,N- dimethylammonio)propane-l-sulfonate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)propionate; 4-(N-hexadecylbenzyl-N,N-dimethylammonio)butyrate;3-(N-tetradecylbenzyl-N,N-dimethylammonio)propane-l-sulfate;3-(N-dodecylbenzylN,N- dimethylammonio)-2-hydroxypropane-l-sulfonate; 3-[N,N-di(dodecylbenzyl)-Nmethylammoniolpropanel-sulfonate;4-[N,N-di(hexadecylbenzyl)-N- methylammonio]butyrate; and 3-[ N,N-di(tetradecylbenzyl)-N-methylammonio]-2- hydroxypropanel -sulfonate.

Zwitterionic surfactants of this type as well as methods for theirpreparation are described in U.S. Pat. Nos. 2,697,116; 2,697,656 and2,669,991 and Canadian Pat. No. 883,864, all incorporated herein byreference.

5. Compounds having the general formula:

R -N c so.

wherein R is an alkylphenyl cycloalkylphenyl or alkenylphenyl groupcontaining from 8 to 20 carbon atoms, in the alkyl, cycloalkyl oralkenyl moiety; R and R are each aliphatic groups containing from 1 to 5carbon atoms; R and R are each hydrogen atoms, hydroxyl groups oraliphatic groups containing from 1 to 3 carbon atoms and R is analkylene group containing from 2 to 4 carbon atoms.

Examples of zwitterionic surfactants of this type include3-(N-dodecylphenyl-N,N- dimethylammonio)propane-l-sulfonate; 4-(N-hexadecylphenyl-N,N-dimethyl )butanel -sulfonate;3-(N-tetradecylphenyl-N,N-dimethylammonio)-3,3-dimethylpropane-l-sulfonate and 3-(N-dodecylphenyl- N ,N-dimethylammonio)-3 -hydroxypropane- 1 sulfonate. Compounds of this type are describedmore fully in British Pat. Nos. 970,883 and 1,046,252, incorporatedherein by reference.

Of all the above-described types of zwitterionic surfactants, preferredcompounds include 3-(N,N- dimethyl-N-alkylammonio)-propane-1-sulfonateand 3(N,N-dimethyLN-alkylammonio)-2hydroxypropanel-sulfonate wherein inboth compounds the alkyl group averages 14.8 carbon atoms in length;3(N,N-dimethyl- N-hexadecylammonio)-propane-l-sulfonate; 3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-lsulfonate;3-(N-dodecylbenzyl-N,N-

dodecylbenzyl-N,N-dimethylammonio)propionate; 6- (N-dodecylbenzyLN,N-dim ethylammonio )hexanoate; and(N,N-dimethyl-N-hexadecylammonio)acetate.

Builder Salts The detergent compositions of the instant inventioncontain, as an essential component, an alkaline, polyvalent anionicdetergent builder salt. In the present compositions these water-solublealkaline builder salts serve to maintain the pH of the laundry solutionin the range of from about 7 to about 12, preferably from about 8 toabout ll. Furthermore, these builder salts enhance the fabric cleaningperformance of the overall compositions while at the same time serve tosuspend particulate soil release from the surface of the fabrics andprevent its redeposition on the fabric surfaces. Surprisingly, althoughthe detergency builder salts serve to suspend clay soils of thekaolinite and illite types and prevent their redeposition on fabrics,they do not appear to interfere with the deposition on fabric surfacesof the smectite-type clay softeners used herein. Furthermore, thesepolyanionic builder salts have been found to cause the smectite-typeclays present in the granular detergent formulations of the invention tobe readily and homogeneously dispersed throughout the aqueous landeringmedium with a minimum of agitation. The homogeneity of the claydispersion is necessary for the clay to function effectively as a fabricsoftener, while the ready dispersability allows granular detegentcompositions to be formulated.

Suitable detergent builder salts useful herein can be of the poly-valentinorganic and poly-valent organic types, or mixtures thereof.Non-limiting examples of suitable water-soluble, inorganic alkalinedetergent builder salts include the alkali metal carbonates, borates,phosphates, polyphosphates, tripolyphosphates, bicarbonates, silicatesand sulfates. Specific examples of such salts include the sodium andpotassium tetraborates, perborates, bicarbonates, carbonates,tripolyphosphates, orthophosphates and hexametaphosphates.

Examples of suitable organic alkaline detergency builder salts are: (l)water-soluble amino polyacetates, e.g., sodium and potassiumethylenediamine tetraacetates, nitrilotriacetates andN-(2-hydroxyethyl)nitrilodiacetates; (2) water-soluble salts of phyticacid, e.g., so dium and potassium phytates; (3) water-solublepolyphosphonates, including, sodium, potassium and lithium salts ofethane-l-hydroxy-l,l-diphosphonic acid; sodium, potassium and lithiumsalts of methylenediphosphonic acid and the like.

Additional organic builder salts useful herein include thepolycarboxylate materials described in U.S. Pat. No. 2,264,103,including the water-soluble alkali metal salts of mellitic acid. Thewater-soluble salts of polycarboxylate polymers and copolymers such asare described in U.S. Pat. No. 3,308,067, incorporated herein byreference, are also suitable herein. It is to be understood that whilethe alkali metal salts of the foregoing inorganic and organicpoly-valent anionic builder salts are preferred for use herein from aneconomic standpoint, the ammonium, alkanolammonium, e.g., triethanolammonium, diethanol ammonium, and the like, water-soluble salts of anyof the foregoing builder anions are useful herein.

Mixtures of organic and/or inorganic builders can be used herein. Onesuch mixture of builders is disclosed in Canadian Pat. No. 755,038,e.g., a ternary mixture of sodium tripolyphosphate, trisodiumnitrilotriacetate and trisodium ethane-l-hydroxy-l,l-diphosphonate.

While any of the foregoing alkaline poly-valent builder materials areuseful herein, sodium tripolyphosphate, sodium nitrilotriacetate, sodiummellitate, sodium citrate and sodium carbonate are preferred herein forthis builder use. Sodium tripolyphosphate is especially preferred hereinas a builder both by virtue of its detergency builder activity and itsability to homogeneously and quickly disperse the smectite claysthroughout the aqueous laundry media without interfering with claydeposition on the fabric surface. Sodium tripolyphosphate is alsoespecially effective for suspending illite and kaolinite clay soils andretarding their redeposition on the fabric surface.

The detergent builders are used at concentrations of from about 10percent to about 60 percent, preferably 20 percent to 50 percent, byweight of the detergent compositions of this invention.

Clay Compounds The fourth essential component of the presentcompositions consists of particular smectite clay materials to providefabric softening concurrently with fabric cleansing. These smectiteclays are present in the detergent compositions at levels from about 1percent to about 50 percent, preferably from 5 percent to l5 percent byweight, of the total compositions. The clays used herein areimpalpable," i.e., have a particle size which cannot be perceivedtactilely. lmpalpable clays have particle sizes below about 50 microns;the clays used herein have a particle size range of from about 5 micronsto about 50 microns.

The clay minerals used to provide the softening properties of theinstant compositions can be described as expandable, three-layer clays,i.e., alumino-silicates and magnesium silicates, having an ion exchangecapacity of at least 50 meg/ g. of clay. The term expandable" as used todescribe clays relates to the ability of the layered clay structure tobe swollen, or expanded, on contact with water. The three-layerexpandable clays used herein are those materials classitied geologicallyas smectites.

There are two distinct classes of smectite-type clays; in the first,aluminum oxide is present in the silicate crystal lattice; in the secondclass of smectites, magne sium oxide is present in the silicate crystallattice. The general formulas of these smectites are Al (Si O (OH) andMg (Si O (OH) for the aluminum and magnesium oxide type clay,respectively. It is to be recognized that the range of the water ofhydration in the above formulas can vary with the processing to whichthe clay has been subjected. This is immaterial to the use of thesmectite clays in the present invention in that the expandablecharacteristics of the hydrated clays are dictated by the silicatelattice structure. Furthermore, atom substitution by iron and magnesiumcan occur within the crystal lattice of the smectites, while metalcations such as Na+, Ca++, as well as H+, can be copresent in the waterof hydration to provide electrical neutrality. Except as notedhereinafter, such cation subsitutions are immaterial to the use of theclays herein since the desirable physical properties of the clays arenot substantially altered thereby.

The three-layer, expandable alumino-silicates useful herein are futhercharacterized by a dioctahedral crystal lattice, while the expandablethree-layer magnesium silicates have a trioctahedral crystal lattice.

As noted hereinabove, the clays employed in the compositons of theinstant invention contain cationic counterions such as protons, sodiumions, potassium ions, calcium ion, magnesium ion, and the like. It iscustomary to distinguish between clays on the basis of one cationpredominantly or exclusively absorbed. For example, a sodium clay is onein which the absorbed cation is predominantly sodium. Such absorbedcations can become involved in exchange reactions with cations presentin aqueous solutions. A typical exchange reaction involving asmectite-type clay is expressed by the following equation:

smectite clay (Na) NH OHZ smectite clay (HN NaOH Since in the foregoingequilibrium reaction, one equivalent weight of ammonium ion replaces anequivalent weight of sodium, it is customary to measure cation exchangecapacity (sometimes termed base exchange capacity) in terms ofmilliequivalents per 100 g. of clay (meg/100 g.). The cation exchangecapacity of clays can be measured in several ways, including byelectrodialysis, by exchange with ammonium ion followed by titration orby a methylene blue procedure, all as fully set forth in Grimshaw, TheChemistry and Physics of Clays, pp. 264-265, Interscience (1971). Thecation exchange capacity of a clay mineral relates to such factors asthe expandable properties of the clay, the charge of the clay, which, inturn, in determined at least in part by the lattice structure, and thelike. The ion exchange capacity of clays varies widely in the range fromabout 2 meg/100 g. for kaolinites to about 150 meg/100 g., and greater,for certain clays of the montmorillonite variety. Illite clays have anion exchange capacity somewhere in the lower portion of the range, i.e.,around 26 meg/100 g. for an average illite clay.

It has been determined that illite and kaolinite clays, with theirrelatively low ion exchange capacities, are not useful in the instantcompositions. Indeed, such illite and kaolinite clays constitute a majorcomponent of clay soils and, as noted above, are removed from fabricsurfaces by means of the instant compositions. However, smectites, suchas nontronite, having an ion exchange capacity of approximately 50 meg/100 g., saponite, which has an ion exchange capacity of around 70meg/100 g., and montmorillonite, which has an ion exchange capacitygreater than 70 meg/100 g., have been found to be useful in the instantcompositions in that they are deposited on the fabrics to provide thedesired softening benefits. Accordingly, clay minerals useful herein canbe characterized as expandable, three-layer smectite-type clays havingan ion exchange capacity of at least about 50 meg/100 g. A smectite-typeclay known as fooler clay, found in a relatively thin vein above theBlack Hills, also has the requisite ion exchange propertiescharacteristic of the clays useful herein and such fooler clay is alsoencompassed by the term smectite-type clay, as used herein.

The smectite clays used in the compositions herein are all commericallyavailable. Such clays include, for example, montmorillonite,volchonskoite, nontronite,

hectorite, saponite, sauconite, and vermiculite. The clays herein areavailable under various tradenames, for example, Thixogel No. 1 (also,Thixo-Jell") and Gelwhite GP from Georgia Kaolin Co., Elizabeth, NewJersey; Volclay BC and Volclay No. 325, from American Colloid Co.,Skokie, Illinois; Black Hills Bentonite BH450, from InternationalMinerals and Chemicals; and Veegum Pro and Veegum F, from R. T.Vanderbilt. It is to be recognized that such smectite-type mineralsobtained under the foregoing tradenames can comprise mixtures of thevarious discreet mineral entities. Such mixtures of the smectiteminerals are suitable for use herein.

While any of the smectite-type clays having a cation exchange capacityof at least about 50 meg/ g. are useful herein, certain clays arepreferred. For example, Gelwhite GP is an extremely white form ofsmectite clay and is therefore preferred when formulating white granulardetergent compositions. Volclay BC, which a smectite-type clay mineralcontaining at least 3 percent of iron (expressed as Fe O in the crystallattice, and which has a very high ion exchange capacity, is one of themost efficient and effective clays for use in laundry compositions andis preferred from the standpoint of product performance. On the otherhand, certain smectite clays marketed under the name bentonite aresufficiently contaminated by other silicate minerals that their ionexchange capacity falls below the requisite range, and such clays are ofno use in the instant compositions.

Appropriate clay minerals for use herein can be selected by virtue ofthe fact that smectites exhibit a true 14A x-ray diffraction pattern.This characteristic pattern, taken in combination with exchange capacitymeasurements performed in the manner noted above, provides a basis forselecting particular smectite-type minerals for use in the granulardetergent compositions disclosed herein.

Optional Components The detergent compositions disclosed herein cancontain other materials commonly used in such compositions. For example,various soil-suspending agents such as carboxymethylcellulose, corrosioninhibitors, dyes, fillers such as sodium sulfate and silica, opticalbrighteners, suds boosters, suds depressants, germicides,anti-tarnishing agents, pl-I adjusting agents such as sodium silicate,enzymes, and the like, well-known in the art for use in detergentcompositions, can also be employed herein. Bound water can also bepresent in said detergent compositions.

Composition Preparation The clay-containing detergent compositions ofthis invention are in granular form. The compositions can beconveniently prepared in standard fashion by admixing the detergentcompound, clay and optional ingredients in a crutcher and spray-dryingthe mixture to form granules. Following this, the quaternary ammoniumanti-static agent can be sprayed on the granules from a melt. It is acritical aspect of this invention to avoid affixing the quaternarycompound to the surface of the clay by an ion exchange mechanism;accordingly, it is preferable to avoid spraying the detergent granuleswith an aqueous solution or suspension of the quaternary compound. Theion-exchange problem is avoided by employing a melt of the quaternarycompound to spray the granules. The compositions are then added to waterto provide a laundering liquor containing the instant compositions tothe extent of from about 0.02 percent to about 2 percent by weight.Soiled fabrics are added to the laundering liquor and cleansed in theusual manner. The effective amount of the detergent compositions to beused will depend to an extent on the weight of clothes being launderedand their degree of soiling. Aqueous laundering baths containing saidcompositions provide adequate cleaning, softening and anti-staticbenefits with soiled fabrics, especially cotton and cotton/polyesterblends. The suspended clay material in the laundering liquor also servesto adsorb fugitive dyes in solution, thereby reducing or inhibiting dyetransfer.

The granular built detergent compositions and processes of the instantinvention are illustrated by the following examples. The following testis used to assess through-the-wash anti-static efficacy of the testproducts.

Anti-Static Test A bundle of mixed fabrics (ca. 53% all-cotton; 12%65/35 polyester/cotton blend; 17% nylon; 18% Dacron") is washed forminutes in a miniature agitator containing two gallons of aqueouswashing liquor containing the test laundry compositions (as set forth,below). The laundering temperature is 100F; water hardness 7 gr/gal.artificial hardness. The bundle comprises 5% by weight of the washingliquor. The bundle is spun dry and rinsed for two minutes in two gallonsof water at 100F and 7 gr/gal. hardness. The fabrics are then dried in acommercial dryer for 50 minutes.

The static charge on each fabric is then measured by a standardelectrostatic technique. The sum of the absolute values of the chargeson all fabrics in the bundle, divided by the sum of the area (yards ofthe total fabric surface (2 sides of the fabric) is then computed. Thisso-called static value, in volts/yd, correlates with gross observationsof the effects of static charges on fabric surfaces, i.e., electricalshocks, fabric clinging, etc. Depending on the fabric bundle tested, nostatic cling is exhibited by fabrics having a static value of less thanabout 1.5 v./yd substantial static cling is noted in fabrics having astatic value above about 4.5 v./yd.

EXAMPLE I Composition A Component Weight Percent Anionic surfactant 16.6Sodium tripolyphosphate 43.3 Sodium silicate 5.8 Sodium sulfate 10.0Gelwhite GP 9 8 Ditallowdimethylammonium chloride 2 0 Miscellaneousminors** Moisture 1.22:1 ratio of sodium tallow alkyl sulfatezsodium Clinear alkyl benzene sulfonate "Including brightencrs.carboxymethylcellulose, coconut alcohol ethoxylate and perfumeComposition A is prepared by admixing all components except theditallowdimethylammonium chloride in a crutcher and spray-drying to formgranules consisting of the surfactant, builder, clay, etc. The granulesEXAMPLE II Composition B Component Weight Percent Anionic surfactant*12.8 Sodium tripolyphosphate 37.8 Sodium silicate 4.5 Sodium sulfate10.8 Volclay BC Ditallow dimethyl ammonium chloride 092 Miscellaneousminors 4.2 Moisture Balance 1.22:1 sodium tallow alkyl sulfatezsodium C,linear alkyl benzene sull'onalc "Including perfume, hrighteners,carhoxymelhylcellulnse and coconut hexaelhoxylate ca. 0.6%

Composition B (prepared in the same manner as Composition A, above) wasemployed in the anti-static test set forth hereinabove. In this test,Composition B was used at a solution concentration of 0.131 percent byweight. Fabrics laundered in the aqueous bath containing Composition Bwere tested for static charge following each of two wash-rinse-dryingcycle. After one cycle, fabrics laundered in Composition B had a staticvalue of 1.2; after two cycles the static value was 1.7. As a point ofcomparison, fabrics laundered in a built, anionic detergent compositionwithout clay or quaternary ammonium salt had a static value of 8.0 afterthe first cycle and 8.6 after the second cycle. Fabrics laundered in abuilt, anionic detergent composition containing a clay softener had ahigher static value than fabrics laundered in liquors without clay.

As can be seen from the foregoing examples, the compositions hereinprovide substantial softening and anti-static benefits. Furthermore, thecompositions herein overcome the problem associated with increasedstatic charge buildup on fabrics laundered with detergents containingclay softeners, alone.

Compositions A and B of the instant invention also provide excellentcleaning and detergency when employed in washing solutions at thespecified concentrations.

Substantially similar detergency, softening and antistatic results areobtained when the anionic surfactant mixture in Compositions A and B isreplaced with an equivalent amount of 2-acetoxy-tridecane-l-sulfonicacid; sodium methyl-a-sulfopalmitate; sodiuma-methoxyoctadecylsulfonate; sodium coconut alkyl ethylene glycol ethersulfonate; and the sodium salt of the sulfuric acid ester of thereaction product of one mole of tallow fatty alcohol and three moles ofethylene oxide, respectively.

Substantially similar detergency, softening and antistatic benefits areobtained when the anionic surfactant mixture in Compositions A and B isreplaced with an equivalent amount of the condensation product of nonylphenol with about 9.5 moles of ethylene oxide per mole of nonyl phenol;the condensation product of coconut fatty alcohol with about 6 moles ofethylene oxide per mole of coconut fatty alcohol; the condensationproduct of tallow fatty alcohol with about 11 moles ethylene oxide permole of tallow fatty alcohol; and the condensation product of asecondary fatty alcohol containing about 15 carbon atoms with about 9moles of ethylene oxide per mole of fatty alcohol, respectively.

Substantially similar detergency, softening and antistatic benefits areobtained when the anionic surfactant mixture in Compositions A and B isreplaced with an equivalent amount of 3(N,N-dirnethyl-N-alkylammonio)-propane-l -sulfonate or 3 (N,N-dimethyl-N-alkylammonio-2-hydroxypropane-lsulfonate wherein in bothcompounds the alkyl group averages 14.8 carbon atoms in length;3(N,N-dimethyl- N-hexadecylammonio)-propane-l-sulfonate; 3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypane-1- sulfonate;3-(N-dodecylbenzyl-N,N- dimethylammonio)-propane-1-sulfonate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)acetate; 3-(N-dodecylbenzyl-N,N-dimethylammonia)propionate; 6-(N-dodecylbenzyl-N,N,dimethylammonio)hexanoate;(N,N-dimethyl-N-hexadecylammonio )-acetate; and sodium3-(dodecylamino)-propane-l-sulfonate, respectively.

Substantially similar detergency, softening and antistatic benefits areobtained when the sodium tripolyphosphate builder in Compositions A andB is replaced with an equivalent amount of sodium nitrilotriacetate;sodium mellitate; sodium citrate; and sodium carbonate, respectively.

Substantially similar detergency, softening and antistatic benefits areobtained when the clay softening agent in Compositions A and B isreplaced with an equivalent amount of volchonskoite; nontronite;hectorite; sauconite; and vermiculite, respectively, all such clayshaving an ion-exchange capacity at least about 50 meg./ 100 g.

Substantially similar detergency, softening and antistatic benefits areobtained when the quaternary ammonium anti-static agent in CompositionsA and B is replaced by ditallowdimethylammonium bromide;ditallowdiethylammonium chloride; dioctadecyldibutylammonium chloride;and ditallowdimethylammonium hydroxide, respectively.

In addition to the fabric softening and anti-static benefits which thebuilt laundry detergent compositions of this invention provide, thecompositions provide still other advantages. For example, thedye-transfer inhibition noted above is a significant advantage notcommonly shared by ordinary laundering and fabric softeningcompositions.

Moreover, the particular class of clays described herein which aredeposited on the fabrics provide a soil-release benefit. The clays areadsorbed by the fabrics being washed providing an improved soil-releasesurface. The benefit from this treatment is that during subsequentwashings, stains and soils are more easily removed from the fabrics ascompared to a fabric which has not previously been exposed to atreatment by the clay-containing compositions of this invention.Furthermore, all of these benefits are enjoyed without impairing thewater-absorbent qualities of the treated fabric. This is in markedcontrast with ordinary quanternary ammonium fabric softeners whichreduce the water-absorbent property of treated fabrics after sev' eralfabric treatments.

It is especially significant that each of the benefits described abovein no way impairs or interferes with the general overall cleaningeffectiveness of the detergent composition, even in compositionscontaining anionic surfactants. The fact that these benefits areattained during the relatively brief span ofa short washing cycle, forexample about 6 to about 15 minutes, is especially noteworthy.

What is claimed is:

1. A granular, built laundry detergent composition, comprising:

a. from about 2 percent to about 30 percent by weight of a non-soapsynthetic detergent compound selected from the group consisting ofanionic synthetic detergents, nonionic synthetic detergents, ampholyticsynthetic detergents, zwitterionic synthetic detergents and mixturesthereof;

b. from about 10 percent to about percent by weight of an organic orinorganic detergent builder salt;

c. from about 1 percent to about 50 percent by weight of a smectite-typeclay softening agent having an ion exchange capacity of at least about50 meg/ g.; and

d. from about 0.5 percent to about 15 weight of a substantiallywater-insoluble quaternary ammonium anti-static agent of the formula [RN R' ],,X", wherein each R is a hydrocarbyl group containing from about10 to about 22 carbon atoms, each R is a hydrocarbyl group containingfrom 1 to about 4 carbon atoms, X is an anion and n is an integer from 1to 3, at a weight ratio of said smectite-type clay to quaternaryammonium antistatic agent of from about 40:1 to about lzl;

said quaternary ammonium compound being in releasable combination insaid composition.

2. A composition according to claim 1 a. wherein the synthetic detergentcompound is an anionic synthetic detergent and is present at from about5 percent to about 20 percent by weight;

b. wherein the builder salt is selected from the group consisting ofalkali metal carbonates, alkali metal borates, alkali metal phosphates,alkali metal polyphosphates, alkali metal tripolyphosphatcs, alkalimetal bicarbonates, alkali metal sulfates, watersoluble aminopolyacetates, water-soluble salts of phytic acid, and water-solublepolyphosponates, and is present at from about 20 percent to about 50 byweight;

c. wherein the smectite-type clay softening agent is selected from thegroup consisting of dioctahedral expandable three-layeralumino-silicates and trioctahedral expandable three-layer magnesiumsilicates and is present at from about 5 percent to about 15 percent byweight; and

(1. wherein the quaternary ammonium anti-static agent is present at aconcentration of from about 0.5 percent to about 5 percent of the totalcomposition.

3. A composition according to claim 1 wherein the smectite claysoftening agent is selected from the group consisting ofmontmorillonites, volchonskoites, nontronites, hectorites, sauconitesand vermiculites.

4. A composition according to claim 1 wherein the anionic surfactant isa water-soluble salt of an organic sulfuric reaction product containingan alkyl group of from about 8 to about 22 carbon atoms and a moietyselected from the group of sulfuric acid ester moieties and sulfuricacid ester moieties.

5. A composition according to claim 1 wherein the builder salt isselected from the group consisting of sodium tripolyphosphate, sodiumnitrilotriacetate, sodium mellitate, sodium citrate and sodiumcarbonate.

6. A composition according to claim 1 wherein the anti-static agent isditallowdimethylammonium chloride.

7. A composition according to claim 6 wherein the smectite-type claysoftening agent is montmorillonite.

8. A composition according to claim 6 wherein the smectite-type claysoftening agent is Gelwhite GP.

9. A composition according to claim 6 wherein the smectite-typesoftening agent is Volclay BC,

10. A granular, built laundry detergent composition, comprising:

a. from about 5 percent to about 20 percent of a mixture, in a 1.22:1weight ratio, ofsodium tallow alkyl sulfate and sodium linear alkylbenzene sulfonate wherein the alkyl chain of the sulfonate averagesabout 12 carbon atoms in length;

b. from about 20 percent to about 50 percent of a sodiumtripolyphosphate builder salt;

0. from about 5 percent to about 15 percent of a member selected fromthe group consisting of Gelwhite GP and Volclay BC clay softeningagents; and

d. from about 0.5 to about 5 percent by weight ofditallowdimethylammonium chloride.

11. A process for simultaneous laundering softening, and providinganti-static benefits to fabrics comprising contacting said fabrics withan aqueous medium containing from about 0.02 percent by weight to about2 percent by weight of a composition in accordance with

2. A composition according to claim 1 a. wherein the synthetic detergentcompound is an anionic synthetic detergent and is present at from about5 percent to about 20 percent by weight; b. wherein the builder salt isselected from the group consisting of alkali metal carbonates, alkalimetal borates, alkali metal phosphates, alkali metal polyphosphates,alkali metal tripolyphosphates, alkali metal bicarbonates, alkali metalsulfates, water-soluble amino polyacetates, water-soluble salts ofphytic acid, and water-soluble polyphosponates, and is present at fromabout 20 percent to about 50 by weight; c. wherein the smectite-typeclay softening agent is selected from the group consisting ofdioctahedral expandable three-layer alumino-silicates and trioctahedralexpandable three-layer magnesium silicates and is present at from about5 percent to about 15 percent by weight; and d. wherein the quaternaryammonium anti-static agent is present at a concentration of from about0.5 percent to about 5 percent of the total composition.
 3. Acomposition according to claim 1 wherein the smectite clay softeningagent is selected from the group consisting of montmorillonites,volchonskoites, nontronites, hectorites, sauconites and vermiculites. 4.A composition according to claim 1 wherein the anionic surfactant is awater-soluble salt of an organic sulfuric reaction product containing analkyl group of from about 8 to about 22 carbon atoms and a moietyselected from the group of sulfuric acid ester moieties and sulfuricacid ester moieties.
 5. A composition according to claim 1 wherein thebuilder salt is selected from the group consisting of sodiumtripolyphosphate, sodium nitrilotriacetate, sodium mellitate, sodiumcitrate and sodium carbonate.
 6. A composition according to claim 1wherein the anti-staTic agent is ditallowdimethylammonium chloride.
 7. Acomposition according to claim 6 wherein the smectite-type claysoftening agent is montmorillonite.
 8. A composition according to claim6 wherein the smectite-type clay softening agent is Gelwhite GP.
 9. Acomposition according to claim 6 wherein the smectite-type softeningagent is Volclay BC.
 10. A granular, built laundry detergentcomposition, comprising: a. from about 5 percent to about 20 percent ofa mixture, in a 1.22:1 weight ratio, of sodium tallow alkyl sulfate andsodium linear alkyl benzene sulfonate wherein the alkyl chain of thesulfonate averages about 12 carbon atoms in length; b. from about 20percent to about 50 percent of a sodium tripolyphosphate builder salt;c. from about 5 percent to about 15 percent of a member selected fromthe group consisting of Gelwhite GP and Volclay BC clay softeningagents; and d. from about 0.5 to about 5 percent by weight ofditallowdimethylammonium chloride.
 11. A process for simultaneouslaundering softening, and providing anti-static benefits to fabricscomprising contacting said fabrics with an aqueous medium containingfrom about 0.02 percent by weight to about 2 percent by weight of acomposition in accordance with claim 1.